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By Nelson Severinghaus

Mineral fillers have been defined as inert materials that are included in a composition for some useful purpose. Because this definition and the scope of this review are not specific-indeed, exceptions abound-accurate total statistics are unavailable. One source estimates the total production in the United States in 1979 at 11.3 Mt (12.5 million st) valued at $534 million, averaging $49.19 per ton. Included are a broad group of minerals-asbestos, barite, bentonite, ground limestone and dolomite, clays, diatomite, feldspar, micas, silica, talc. Additional references will be made to synthetic mineral-derived fillers such as aluminum hydrate, precipitated calcium carbonate, and pyrogenic and precipitated silicas and silicates. A section on related uses at the end of this chapter covers absorbents and filters. Mineral fillers can be included in compounds to accomplish a variety of final results. Hardness, brittleness, impact strength, compressive strength, softening point, fire resistance, surface texture, electrical conductivity, and a host of other physical characteristics may be modified by the inclusion of fillers. These effects are the result of properties of the fillers, including chemical activity, hardness, particle size, shape and distribution, surface structure, color, density, and refractive index. To facilitate an overview of the mineral filler industry, this chapter will review the general usage of fillers, the inherent characteristics that intensify their utilization, and similarly their manufactured characteristics. Major using industries will then be examined in detail. Specific information on deposits and processing for industrial minerals will be found in the appropriate commodity chapter. All of these same minerals have additional significant uses based on their chemical composition or other characteristics. References will be found in other use chapters and summarized in commodity chapters. The chart in Table 1, updated from the 4th edition of Industrial Minerals and Rocks, illustrates the major mineral fillers (both natural and manufactured) and their more important end uses. Use of Mineral Fillers Archaeologists have found that more than 5000 years ago, bitumen used for mortar and waterproofing contained mineral contaminants that acted as fillers. Since that time man has added mineral products to compounds to improve certain characteristics. Perhaps the most common objective of filler usage is reduction of cost of the end product. Certainly the inclusion of a filler that costs 2¢ per 0.45 kg (lb) will reduce the cost of a plastic product whose resin costs 50¢ per 0.45 kg (lb). But the decision to use a specific filler is not that simple. It may "soak up" binder, making a compound more viscous and perhaps preventing its flow into a mold as an injection molding compound, but similarly will give good anti-sag characteristics to putty, caulking compound, or undercoating. Fillers may be incorporated to modify: 1) Cost 2) Physical characteristics 3) Flow characteristics 4) Fire resistance 5) Density 6) Heat conductivity 7) Color or brightness and opacity 8) Hardness, brittleness, impact strength 9) Deformity, viscosity, softening point 10) Processing problems 11) Electrical conductivity 12) Surface texture 13) Thermal expansion characteristics 14) Abrasion resistance

Jan 1, 1983

By B. A. Rogers, K. O. Stamm

BECAUSE it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,1 which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has developed recently concerning the reversibility of the transformation. From thermodynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912° for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9180 and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rates of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°°C. and concluded that a change occurs reversibly between 907° ± 3° and 9100 ± 3°C., probably between 907° and 910°C. Wells, Ackley, and Mehl6 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, '1/2°, and 1/8°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909.5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien elements were low enough, the A3 transformation would be completely reversible at 909.5° ± I°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1941

By K. O. Stamm, B. A. Rogers

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By B. A. Rogers, K. O. Stamm

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By A. N. Holden, J. H. Hollomon

Inhomogeneous yielding during the early stages of plastic flow has been observed in many metals and has long been a subject of controversy. Low carbon steel, when strained at room temperature, exhibits a distinct yield point at which the metal ceases to behave elastically and begins to flow plastically without further increase in stress,† often with an actual decrease in stress from that existing at the yield point. One manifestation of this behavior is the familiar Lüders lines. The extent of the yield point elongation (the plastic strain which results without raising the stress above that at the initial yield point) may be several percent. Several explanations of this type of yielding in steels have appeared in the literature:1-3}; 1. The segregation of carbides or other constituents at the grain boundaries of ferrite forms cell-like blocks which break down at a higher stress than that at which the ferrite alone will flow. 2. The precipitation of various constituents within the ferrite itself in some way blocks initial flow until a higher stress is reached, after which a great deal of flow occurs without further increase in stress. 3. The restraining influence of neighboring, less favorably oriented grains in a polycrystal results in a storing up of energy, which on yielding is sufficient to cause the continued propagation of slip bands on the multiplicity of slip systems available in adjacent iron crystals without increase in stress. 4. Local segregation of carbon atoms increases the stress required for the initial propagation of dislocations. The stress required for further deformation is lower.3 Such an explanation would require the presence of upper and lower yield points in single crystals. Low and Gensamer2 have shown that heterogeneous yielding can be eliminated by removal of carbon and nitrogen from polycrystalline steels by wet-hydrogen treatment. They also demonstrated that the re-introduction of minute amounts of carbon or nitrogen caused a return of the yield point. Observations of the initial flow of single crystals containing small amounts of carbon and nitrogen- should provide a clue to the explanation of inhomogeneous yielding. Previous tests of iron crystals4-6 can not be considered conclusive because it is uncertain whether the carbon and nitrogen were satisfactorily removed by the decarburization technique employed. The purpose of the experiments described herein was to determine whether single iron crystals containing either carbon or nitrogen would exhibit in-homogeneous yielding. Experimental Procedures THE PREPARATION OF SINGLE CRYSTALS All crvstals were formed in the following way. Aluminum killed sheet material 80 mils thick was machined into specimens of the outer contour shown in Fig 1. These mildly tapered specimens were decarburized at 730°C for 16 hr in hydrogen that had been bubbled rapidly through water maintained at 70°. The resultant grain size after decarburizing was approximately ASTM 5. Several stress-strain curves were made of the decarburized niate-

Jan 1, 1950

By N. A. Gokcen

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams' that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K'1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK'1 - XK'1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-

Jan 1, 1954

The Palabora ore consists of two types, a carbonatite containing a low titanium magnetite, and a foskorite containing high titanium magnetite. The latter type also contains substantial quantities of phosphate. These two ore types are separately crushed and are kept separate through copper flotation and magnetic separation, for recovery of magnetite, with the low Ti magnetite being shipped as iron ore. High phosphate tailings are pumped to Foskor, a government-owned phosphate plant nearby. The Palabora plant was originally designed in 1966 for 33, 000 tpd using two 54 in. by 74 in. Allis -Chalmers gyratories; two 7 ft (2. 13 m) standards; four 7 ft shortheads; and six grinding lines, each using one 1,200 hp rod mill and two 1,200 hp ball mills. A fifth short- head and one more grinding line were added later; and with flowsheet improvements, the capacity of the plant was increased to 59, 500 stpd. A further plant expansion involving a third 54 in. primary and two 32 ft by 15 ft (9.75 by 4.6 m) 9,000 hp autogenous mills and another flotation section will bring its capacity to 87,500 stpd in 1977. These two fully autogenous mills are constructed entirely out of doors near the primary crusher, and the ground ore will be pumped a mile to the concentrator by a five-stage pumping system. The Palabora ore is mined with 6, 10, and 12 7d (4.6, 7.6, and 9. 2 cu m) shovels and hauled to the crushers in 110 and 165 st trucks. Sixty-five ton trucks were originally used, but the crusher dump pockets were designed for larger units. Dump pockets, crushers, feeders, and take- away belts are offset in order to keep the two ore types separate. Centerlines of the crushers are only 43 ft (13. 1 m) apart; but, because of their being offset, maintenance room is ample. Initially, more carbonatite ore than foskorite was mined; but as the pit has deepened, this ratio has been reversed. The Palabora ore breaks in the pit with a large amount of oversize boulders; and, with the use of larger trucks, a splitter has been installed on one side of each dump pocket to protect the crusher spider. Smaller trucks dump on the opposite side. To accomodate the splitter, the pocket edge has been raised one meter and moved back one meter. Dust is collected through a special vent shaft between the crushers and the mantle relining area; but even so, two high-pressure water spray headers with nozzles are installed under the edge of the pocket at each dumping position. While only one truck dumps at a time, sprays from all four headers are used to suppress dust. Any leakage of water through the seal around the upper bowl of the crusher is caught by a circular trough under the seal and directed to a sump pump. At this point, there

Jan 1, 1978

By G. H. Anderson

Cadmium-coppeR precipitate, a byproduct of the purification stage of the zinc plant, is composed mainly of zinc, cadmium and copper in varying amounts depending on the efficiency of precipitation and the cadmium and copper contents of the impure solution treated. The composition range is approximately: cadmium 10-12 pct, copper 6-8 pct, and zinc 3&35 pct. As received at the cadmium plant, the precipitate is a dark gray to black press cake produced by filter pressing the flocculent cadmium-copper precipitate formed when impure zinc solution is agitated with zinc dust. The details of the cadmium-copper precipitation are to be found in the paper "Electrolytic Zinc at Risdon, Tasmania," by W. C. Snow. Transactions AIME, 121, 501. The treatment, in addition to recovering cadmium as metal, yields a copper product as a residue for realization and recovers in solution for return to the zinc plant, the excess of zinc dust used during purification. The recovery of cadmium metal is approximately 200 tons† per year, but, with the amount of copper residue recovered, varies with the zinc production tonnage, composition of the original concentrates, degree of roasting and other operational factors. The operations involved in the recovery of the foregoing materials are carried out in a building adjacent to the purification section of the zinc plant and can best be described by dividing the process into the following stages: 1. Oxidation and Grinding of the cadmium-copper precipitate. 2. Leaching and Filtering. 3. Precipitation of cadmium. 4. Oxidation and Grinding of the precipitated cadmium. 5. Leaching oxidized cadmium precipitate and Purification of leach solution. 6. Electrolysis. 7. Melting, Casting and Packing. A feature of the process is the use of two distinct solution circuits. Spent electrolyte from the zinc plant circuit containing about 10 pct sulphuric acid is used as the primary solvent of the cadmium and zinc present in the oxidized precipitate. When the cadmium is later separated by precipitation and filtering, the filtrate, originally zinc plant spent electrolyte and now fortified in zinc, is returned to the zinc plant. The precipitated cadmium, after oxidation, is redissolved in spent electrolyte from cadmium electrolysis which solution is in closed circuit within the cadmium plant except for discards to the zinc plant circuit as mentioned in Section 5 hereinafter. (Fig 1.) Details of the various operations follow. I. Oxidation and Grinding of the Cadminm-copper Precipitate The precipitate having had a preliminary drying by compressed air in Dehne filter presses in the zinc plant is trucked to a storage platform of sufiicient length to store 3 to 4 days' production separately. After 48 hr exposure to atmosphere, oxidation is sufficient to enable all cadmium and zinc but only a portion of the copper to be dissolved in dilute sulphuric acid. The oxidized precipitate is shovelled into trucks and, after weighing and sampling, is broken in size by means of

Jan 1, 1950

President H. M. Howe, Boston, Mass. (communication to the Secretary): Le Chatelier's pyrometer is certainly a most convenient and accurate instrument for the laboratory, and one that may be used under some conditions in the mill. I have used it for several years and with great satisfaction. Like Prof. Roberts-Austen and unlike Herr Blass, I have always found that its indications remain constant over long periods. Like Prof. Roberts-Austen, also, I find it possible, in a quiet place, to read with extreme accuracy ; and, by the use of a telescope, I can read temperatures to within a degree, for some delicate determinations which I have in hand. Variations in the temperature of the room affect the readings of the instrument far less than one would expect. When the current is cut off, the mirror does not always return exactly to the same place; in other words, the zero shifts appreciably, and must be determined often, indeed every few hours if accuracy be desired. In some cases I have had it determined within a very few minutes of every important reading. To this end a switch should he introduced, so that the circuit may be broken readily. With this arrangement we can determine accurately the position of the zero within a very few seconds of the time of taking any especially important reading. The chief causes of the variation of the zero which I have noticed are as follows: a. The suspension may not be tight enough, so that the momentum of the galvanometer frame as it swings makes its supporting wires slip in their bearings. b. Changes in the position of neighboring iron objects may deflect the mirror. c. Changes in the temperature of the room may, perhaps, change the torsion of the suspension wires, and so shift the mirror. d. Dust may attach itself to the galvanometer frame, and by friction against the surrounding fixed parts of the galvanometer, may

Jan 1, 1895

By L. J. M. Smits

A theoretical equation is developed describing membrane potentials of shaly sands as a function of the cation-exchange capacity per unit pore volume of the rock and saturating water salinity. This equation is based on the same simple physical model as that employed earlier7 describing the electrical conductivity of shaly sands. Experiments conducted with NaCl solutions showed that the equation is obeyed, except in the case of saturated salt solutions where minor deviations were observed. A possible explanation is given for this discrepancy. As the clay content and the porosity of shales may vary appreciably, shale membrane potentials also vary. It was found that membrane potentials of shales can be calculated accurately with the aid of the same theory. Consequently, changes in membrane potentials can be accounted for by simple measurement of cation-exchange capacities per unit pore volume of both shales and shaly sands. Charts are given to facilitate interpretation of the electrochemical part of the SP in terms of cation-exchange capacities and the salinities of mud filtrate and formation water. INTRODUCTION A spontaneous potential (SP) log is a record of the way in which the electrical potential of a sonde varies as it passes down a borehole. Such variations frequently reflect rock texture, e.g., permeable beds intercalated in an impermeable series often are indicated by a sharp change in potential. Nowadays it is recognized that SP logs may be interpreted in terms of formation-water salinity and formation shaliness. The four sources of the SP are illustrated in Fig. 1. El and E4 represent streaming potentials generated by the flow of mud filtrate through mud cake opposite permeable formations and through shale, respectively. An extensive review of the literature on the evaluation of these streaming potentials is given by Lynchl and will not be discussed here. The remaining part of the SP generally is called the electrochemical potential, which is divided into two parts: a membrane potential across the shale (E3, Fig. 1) and a membrane potential in the permeable sand at the diffusion boundary between formation water and mud filtrate (E2, Fig. 1). It was found by wyllie2 that the membrane potential across the shale, E3, is the most important contribution to the electrochemical potential, the shale acting as a semi permeable membrane. When the sand is clean it does not influence the diffusion process, so E2 equals the value of the so-called liquid-liquid junction potential observed when the two solutions diffuse freely into each other. When the sand contains clay, however, this interferes with the diffusion process and affects the diffusion potential generated. The greater the proportion of clay, the stronger this effect will be. Wyllie,3 Doll4 and Poupon et al.5 took this effect into account theoretically, starting from a physical

Jan 1, 1969

By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.' During quenching, nearly all of the silver segregates into zones' and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y' and y precipitates.' The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y' plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155' and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7' was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y' precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By R. I. Jaffee, J. G. Dunleavy, H. R. Ogden, Webster Hodge

INTRODUCTION EARLY in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fick1 and Ruer and Goerens2 definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line off immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 1570°C in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Ford5 have shown that, when hot-rolled copper iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have 150,000 psi tensile strength, and about 41 pct IACS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult, In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation 0f this type of alloy. As a result 0f this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1948

By R. T. Webber, R. B. Owen

The vapor phase deposition of molybdenum and tungsten from the hexacar-bonyls has been thoroughly investigated by Lander and Germerl, and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2'3 could be similarly deposited, but did not investigate this metal extensively. Recently, conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. Apparatus and Technique The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T² and T3 containing crystals of the carbonyl. T² is kept in a constant temperature bath (not shown), while T³ is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Se, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by Sb is used to determine the volume included by S4, S6, SB, Slot the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: (I) the specimen temperature, from room temperature to about 1000°C, (2) the carbonyl vapor pressure, from 40 to 220 microns, and (3) the hydrogen flow. In several runs, 0.8 to 1.8 PCt of hydrogen sulfide was introuced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1949

By T. E. Leontis, D. H. Feisel

MAGNESIUM alloys containing rare earth metals have received considerable attention during the past several years because of the need for light alloys having high strength and creep resistance at elevated temperatures. Although much of the work reported earlier has dealt with alloys containing Mischmetal, it has been shown in two previous papersl, V hat distinctly different effects are produced by various rare earth metals and rare earth metal mixtures on the properties of magnesium. For example, much higher strengths are obtained in magnesium alloys containing didym-ium (essentially neodymium plus praseodymium) than in alloys made with Mischmetal, which contains all the rare earth metals in the proportions in which they occur naturally in the monazite ore. Mg-rare earth metal alloys are characterized by a relatively coarse grain size, which greatly impairs castability. The addition of zirconium as a second alloying ingredient has been shown8,7 to refine the grain size, which also produces a distinct improvement in the strength properties. Certain Mg-Mischmetal-Zr and Mg-Mischmetal-Zn-Zr alloy compositions which are currently being produced commercially have been discussed in dytail by Nelson and Strieter,8,4 who also present some in- formation on a Mg-low Ce-Mischmetal-Zr alloy, and by Nelson.8 A patent issued to Jessup, Emley, and Fisher9 emphasizes the superiority of Mg-didymium-Zn-Zr alloys over the corresponding alloys made with Mischmetal. The purpose of this paper is to present the results of an extensive investigation concerned with the effect of increasing amounts of zirconium on magnesium sand casting alloys containing several different rare earth metal mixtures in varying amounts. The effect of the addition of zinc to some of these alloys is also being reported. Preparation and Testing of Alloys The alloys studied in this investigation were prepared in small laboratory melts according to the melting procedures described by Nelson1" as the Crucible Method. Electrolytic magnesium having the composition shown in Table I was used as the starting material. The rare earth metal alloying ingredients used in preparing these alloys were essentially of the compositions listed in Table 11. Some of the didymium-containing alloys were prepared using a Mg-didymium hardener. The rare earth metal content of this hardener analyzed 1.2 pct Ce, 10.4 pct Pr, 80.8 pct Nd, and 7.6 pct La. The zirconium was added in one of three forms: 1) as sponge zirconium obtained from the Bureau of Mines; 2) as a fused salt consisting of 50 pct ZrCl, and 50 pct alkali chlorides from which the zirconium is reduced by the magnesium; or 3) as a Mg-Zr hardener. The alloying procedures and melt hand-

Jan 1, 1958

By N. P. Peterson

The Castle Dome copper deposit is of the porphyry type and occurs in a body of quartz monzonite intruded into the pre-Cambrian formations and possibly into the lower part of Paleozoic limestones. The hypogene sulphide minerals include pyrite, chalcopyrite, and a little molybdenite, sphalerite, and galena. Pyrite and chalcopyrite are disseminated or occur in small closely spaced veins. The hypogene mineralization shows distinct zoning in the distribution of pyrite and chalcopyrite, so that the mineralized area can be subdivided into pyritc and chalcopyrite zones. Supergene enrichment, though not extensive, played an important part in the formation of the ore body, the chalcopyritc zone being the pro-tore. Several thin, gently dipping, diabase sills occur in the mineralized area, and the copper content of the rock in and near these sills is substantially higher than average. The formation of the ore body was caused by the combined effects of three forces: I. Zoning of the hypogene mineralization, 2. Richer copper metallization associated with the diabase sills, and 3. Supergene enrichment. Introduction The Castle Dome copper deposit is about 5 miles west of Miami, Arizona, and about 3 miles west of the Miami-Inspiration ore body. The Castle Dome open-pit mine is on the south flank of Porphyry Mountain, a prominent landmark of the region. In 1941 the deposit was being explored by the Miami Copper Co., but the exploration program was cut short when the decision was made to develop the property as a war project. The Castle Dome Copper Co., Inc., was organized as a wholly owned subsidiary of the Miami Copper Co., and arrangements were made with Defense Plant Corp. for developing and equipping the mine and for construction of a concentrating plant. Construction and development work was begun in January 1942, and milling operations started June so, 1943. Since that date, the mine has been in continuous operation by the Castle Dome Copper Co, under a lease agreement with Defense Plant Corp. producing copper at an average rate of 4,000,000 lb per month. To January I, 1946 the total production amounted to 121,088,000 lb of copper,4,271 oz of gold, and 211,755 oz of silver. A detailed study of the copper deposit and the surrounding area was undertaken by the U. S. Geological Survey in June 1943. Other members of the Survey participating in the work were C. M. Gilbert, G. L. Quick, and J. P. Albers. The results of this work will be published as a comprehensive report by the Geological Survey. General Geology The Globe quadrangle, which includes the Castle Dome area, was studied by F. L. Ransome1 of the Geological Survey in 1901 and 1902. His maps and descriptions were

Jan 1, 1949

By N. P. Peterson

The Castle Dome copper deposit is of the porphyry type and occurs in a body of quartz monzonite intruded into the pre-Cambrian formations and possibly into the lower part of Paleozoic limestones. The hypogene sulphide minerals include pyrite, chalcopyrite, and a little molybdenite, sphalerite, and galena. Pyrite and chalcopyrite are disseminated or occur in small closely spaced veins. The hypogene mineralization shows distinct zoning in the distribution of pyrite and chalcopyrite, so that the mineralized area can be subdivided into pyritc and chalcopyrite zones. Supergene enrichment, though not extensive, played an important part in the formation of the ore body, the chalcopyritc zone being the pro-tore. Several thin, gently dipping, diabase sills occur in the mineralized area, and the copper content of the rock in and near these sills is substantially higher than average. The formation of the ore body was caused by the combined effects of three forces: I. Zoning of the hypogene mineralization, 2. Richer copper metallization associated with the diabase sills, and 3. Supergene enrichment. Introduction The Castle Dome copper deposit is about 5 miles west of Miami, Arizona, and about 3 miles west of the Miami-Inspiration ore body. The Castle Dome open-pit mine is on the south flank of Porphyry Mountain, a prominent landmark of the region. In 1941 the deposit was being explored by the Miami Copper Co., but the exploration program was cut short when the decision was made to develop the property as a war project. The Castle Dome Copper Co., Inc., was organized as a wholly owned subsidiary of the Miami Copper Co., and arrangements were made with Defense Plant Corp. for developing and equipping the mine and for construction of a concentrating plant. Construction and development work was begun in January 1942, and milling operations started June so, 1943. Since that date, the mine has been in continuous operation by the Castle Dome Copper Co, under a lease agreement with Defense Plant Corp. producing copper at an average rate of 4,000,000 lb per month. To January I, 1946 the total production amounted to 121,088,000 lb of copper,4,271 oz of gold, and 211,755 oz of silver. A detailed study of the copper deposit and the surrounding area was undertaken by the U. S. Geological Survey in June 1943. Other members of the Survey participating in the work were C. M. Gilbert, G. L. Quick, and J. P. Albers. The results of this work will be published as a comprehensive report by the Geological Survey. General Geology The Globe quadrangle, which includes the Castle Dome area, was studied by F. L. Ransome1 of the Geological Survey in 1901 and 1902. His maps and descriptions were

Jan 1, 1949

By C. V. Millikan, Herbert F. Beardmore

Declining Productivity Index, as considered herein, is a productivity index that has a substantially and consistently decreasing value when measured over a period of a few hours. If not recognized, it may be interpreted as representing an unsettled or unstable condition in a producing well. It forms the basis of a number of predictions as to future performance compared with the performance of wells in which the productivity index does not decline. The nost important of these are that: (I) the rate of oil production will decline more rapidly, (2) the gas-oil ratio will usually increase abnormally, (3) the amount of water ultimately produced will be negligible, if any, (4) stop-cocking will increase current production and decrease gas-oil ratio. When such relative well performance is indicated, it follows that certain reservoir performance and operating practices may be anticipated: (I) disappointing recovery, (2) longer natural flow, (3) no active water drive, (4) better evaluation of acidizing, shooting and reworking, (5) intermittent operation of wells, (6) smaller pumping equipment required. It is significant that the basis of these important predictions is bottom-hole pressure tests that can be made immediately after completion of the wells. Introduction "'Productivity index" is the number of barrels of oil produced per day per pound per square inch of differential pressure between the reservoir and the bottom of the well. "Declining Productivity Index," as considered herein, is a productivity index that has a substantially and consistently decreasing value when measured over a period of a few hours. Productivity index can be determined only when the rate of production can be stabilized. In most wells the rate of production and bottom-hole pressure are easily stabilized to give a constant productivity index for a period of many hours. A few produce so erratically as to preclude probability of an acceptable test in the usual sense. A satisfactory productivity index can be determined in some wells only by gauging the production accurately by hours, measuring the bottom-hole pressure continuously, and from these data calculating the productivity index for successive hours. Such figures frequently will have a decreasing value—that is, a declining productivity index—and when plotted on double. logarithmic cross-section paper with productivity index as ordinate and time as abscissa will be a straight-line curve. The angle between the curve and the abscissa is referred to as the rate of decline. Declining productivity index may appear to be the result of change in permeability to oil due to decreasing saturation of oil and increasing saturation of gas in the reservoir. It is possible that such is in fact the cause, but if so, more is involved than merely relative saturation of oil and gas. This seems evident because the rate of decline in productivity index is substantially the same regardless of the pro-

Jan 1, 1945

By R. I. Jaffee, J. G. Dunleavy, W. Hodge, H. R. Ogden

Early in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fickl and Ruer and Goerensz definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line of immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 157oOC in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Fords have shown that, when hot-rolled copper-iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have I50,000 psi tensile strength, and about 41 pct I.\CS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult. In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation of this type of alloy. As a result of this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1949

By R. W. Heckel, H. P. Cheskis, A. Lawley, M. R. Pinnel

THERE are discrepancies reported in the literature regarding the micro and macro stress-strain behavior of metals and alloys. In particular, Young's modulus and micro yield measurements often show significant variations depending upon the techniques employed.'-" The purpose of this note is to correlate measurements made with four techniques and to indicate where some of these discrepancies might arise. Allied use of these techniques can provide a complete and consistent characterization of micro and macro stress-strain behavior (over the strain range of 10-9 to 10--2 in. in.-') from a minimum number of samples. Techniques. The techniques employed for measuring stress-strain behavior involved the use of a) linear differential transformers, b) SR-4 strain gages, c) longitudinal resonance waves, and d) X-ray diffraction. Specimen geometries and preparations are summarized in Table I for each technique. Differential Transformer and Strain Measurements. An Instron universal testing machine, modified with an alignment device, was used to apply the load via parallel-jaw grips. The signal from the load cell was applied to the Y scale of a Moseley X-Y recorder (sensitivity of 10 lb load per in. chart). The elongation was monitored simultaneously with strain gages mounted on three sides of the rectangular specimen, and with two linear variable differential transformers (LVDT) mounted at 90 deg to one another on faces that also contained the strain gages, Fig. 1. The signal from one of the LVDT's was applied to the X scale of the recorder (sensitivity 40 µ in. elongation per in. chart) in order to trace a continuous load-elonga-tion curve. Concurrently, the strain on the same face (i.e., the face monitored by the LVDT) was recorded by the corresponding strain gage. A stress-strain curve was plotted from the load cell-strain gage data and was compared to the stress-strain curve (converted from load-elongation) plotted from the continuous load cell-LVDT trace. Identical Table I. Description of Specimens Used in the Present Study Material Dimerisions Preparation Condition 99.99 pct A1 tensile 318 by 3/16 by 3 in. as cast ingot; cut annealed specimen on diamond wheel 2024 A1 tensile 318 by 3/20 by 31/2 in. vacuum hot annealed specimen pressed sheets; cut on diamond wheel 99.99 pct Al 3116 by 3/16 by 2 in. cut from tensile prestrained dynamic modulus specimen after 10"* in. specimen test per in. 2024 A1 dynamic 3/20 by 3/20 by 2 in. vacuum hot annealed modulus specimen pressed sheets; cut on diamond wheel 2024 A1 X-ray gage section 112 by vacuum hot annealed specimens 1/4by1/20in. pressed sheets; cut on diamond wheel

Jan 1, 1970

By R. S. Sandhu, L. E. Baker, W. Y. Shieh

The finite element method of analysis was introduced by Clough.1 Within a short period, it has developed into a powerful solution technique in structural and continuum mechanics. It has been used to solve boundary value problems in two and three-dimensional elasticity.2-5 Anisotropy and heterogeneity of materials were allowed for at the earliest stages. 1,4 Its application has been extended to allow for cracks,5 creep and viscoelasticity, 6,7 incremental construction,6-8 nonlinear elasticity3,9 effect of joints in rock,10 and to materials with different behavior in tension and compression.7 Because of its versatility, the finite element method has found increasing application in the field of rock mechanics. In fact, several of the more significant developments have been motivated by problems in this field. Elasto-plastic material behavior based on the incremental or rate-type theory of plasticity rather than the deformation theory was considered by Reyes and Deere11 A material law based on a generalization 12 of the Mohr-Coulomb criterion was used. In this chapter, the formulation of material laws developed by Reyes and Deere 11 is used. An efficient analysis procedure, incorporating recent developments in finite element analysis, is developed for plane-strain conditions. To demonstrate its effectiveness, the procedure is applied to three cases, one for which an exact solution is available, another for which field observations had been made, and a third one for which a parallel study was made, using an accepted limit-equilibrium method.

Jan 1, 1970